+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

The Mn cluster in the S(0) state of the oxygen-evolving complex of photosystem II studied by EXAFS spectroscopy: are there three Di-mu-oxo-bridged Mn(2) moieties in the tetranuclear Mn complex?



The Mn cluster in the S(0) state of the oxygen-evolving complex of photosystem II studied by EXAFS spectroscopy: are there three Di-mu-oxo-bridged Mn(2) moieties in the tetranuclear Mn complex?



Journal of the American Chemical Society 124(25): 7459-7471



A key component required for an understanding of the mechanism of the evolution of molecular oxygen by the photosynthetic oxygen-evolving complex (OEC) in photosystem II (PS II) is the knowledge of the structures of the Mn cluster in the OEC in each of its intermediate redox states, or S-states. In this paper, we report the first detailed structural characterization using Mn extended X-ray absorption fine structure (EXAFS) spectroscopy of the Mn cluster of the OEC in the S(0) state, which exists immediately after the release of molecular oxygen. On the basis of the EXAFS spectroscopic results, the most likely interpretation is that one of the di-mu-oxo-bridged Mn-Mn moieties in the OEC has increased in distance from 2.7 A in the dark-stable S(1) state to 2.85 A in the S(0) state. Furthermore, curve fitting of the distance heterogeneity present in the EXAFS data from the S(0) state leads to the intriguing possibility that three di-mu-oxo-bridged Mn-Mn moieties may exist in the OEC instead of the two di-mu-oxo-bridged Mn-Mn moieties that are widely used in proposed structural models for the OEC. This possibility is developed using novel structural models for the Mn cluster in the OEC which are consistent with the structural information available from EXAFS and the recent X-ray crystallographic structure of PS II at 3.8 A resolution.

Please choose payment method:






(PDF emailed within 1 workday: $29.90)

Accession: 011470252

Download citation: RISBibTeXText

PMID: 12071755


Related references

The state of manganese in the photosynthetic apparatus. 4. Structure of the manganese complex in Photosystem II studied using EXAFS spectroscopy. The S1 state of the O2-evolving Photosystem II complex from spinach. Biochimica et biophysica acta 850(2): 324-332, 1986

Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of photosystem II. Biochemistry 41(43): 12928-12933, October 29, 2002

Orientation of the Tetranuclear Manganese Cluster and Tyrosine Z in the O 2 -Evolving Complex of Photosystem Ii: An Epr Study of the S 2 Y Z State in Oriented Acetate-Inhibited Photosystem Ii Membranes. Biochemistry 38(39): 12758-12767, 1999

Orientation of the tetranuclear manganese cluster and tyrosine Z in the Q2-evolving complex of photosystem II: an EPR study of the S2YZ. state in oriented acetate-inhibited photosystem II membranes. Biochemistry (American Chemical Society) 38(39): 758-67, 1999

Correlation between structure and magnetic spin state of the manganese cluster in the oxygen-evolving complex of photosystem II in the S-2 state: Determination by X-ray absorption spectroscopy. Biochemistry 33(16): 4923-4932, 1994

High-resolution Mn EXAFS of the oxygen-evolving complex in photosystem II: structural implications for the Mn4Ca cluster. Journal of the American Chemical Society 127(43): 14974-5, 2005

Tetranuclear [Mn III Mn 3 IV O 4 ] Complexes as Spectroscopic Models of the S 2 State of the Oxygen Evolving Complex in Photosystem II. Journal of the American Chemical Society 2018, 2018

Orientation of calcium in the Mn4Ca cluster of the oxygen-evolving complex determined using polarized strontium EXAFS of photosystem II membranes. Biochemistry 43(42): 13271-13282, 2004

New linear high-valent tetranuclear manganese-oxo cluster relevant to the oxygen-evolving complex of photosystem II with oxo, hydroxo, and aqua coordinated to a single Mn(IV). Inorganic Chemistry 44(25): 9567-9573, 2005

Structural Change of the Mn Cluster during the S 2 →S 3 State Transition of the Oxygen-Evolving Complex of Photosystem II. Does It Reflect the Onset of Water/Substrate Oxidation? Determination by Mn X-ray Absorption Spectroscopy. Journal of the American Chemical Society 122(14): 3399-3412, 2000

Redox changes of the oxygen evolving complex in photosystem II core particles as studied by UV spectroscopy. Murata, N Research in photosynthesis, Vol II: 325-328, 1992

Temperature dependence of the S-1 fwdarw S-2 transition in the oxygen-evolving complex of photosystem II studied by FT-IR spectroscopy. Biochimica et Biophysica Acta 1143(3): 333-336, 1993

Temperature dependence of the S1 leads to S2 transition in the oxygen-evolving complex of photosystem II studied by FT-IR spectroscopy. Biochimica et biophysica acta = International journal of biochemistry and biophysics6, 1143(3): 333-336, 1993

Is chlorine ligated to Mn in the oxygen-evolving complex in photosystem II? Results of EXAFS studies oriented Br-substituted photosystem II. Biophysical Journal 68(2 PART 2): A366, 1995

Electronic structure of S(2) state of the oxygen-evolving complex of photosystem II studied by PELDOR. Biochimica et Biophysica Acta 1827(3): 438-445, 2013